Benzisoxazolo(thiono)phosphoric(phosphonic)acid esters

ABSTRACT

BENZISOXAZOLO (THIONO) PHOSPHORIC (PHOSPHONIC) ACID ESTERS OF THE GENERAL FORMULA   3-(RO-P(=X)(-R1)-O-)-1,2-BENZISOXAZOLE   IN WHICH R IS A LOWER ALKYL RADICAL, R1 IS A LOWER ALKYL OR ALKOXY RADICAL, AND X IS AN OXYGEN OR SULFUR ATOM, WHICH POSSESS OMSECTICIDAL, ACARICIDAL, NEMATOCIDAL AND, IN SOME CASES, FUNGICIDAL PROPERTIES.

United States Patent Office US. Cl. 260-307 2 Claims ABSTRACT OF THEDISCLOSURE Benzisoxazolo (thiono) phosphoric (phosphonic) acid esters ofthe general formula in which R is a lower alkyl radical,

R is a lower alkyl or alkoxy radical, and X is an oxygen or sulfur atom,

which possess insecticidal, acaricidal, nematocidal and, in some cases,fungicidal properties.

The present invention relates to and has for its objects the provisionof particular new benzisoxazolo(thiono) phosphoric(phosphonic) acidesters, which possess insecticidal, acaricidal, nematocidal andfungicidal properties, active compositions in the form of mixtures ofsuch compounds with solid and liquid dispersible carrier vehicles, andmethods for'produ'cing such compounds and for using such compounds in anew way especially for combating pests, e.g. insects, acarids, nematodesand fungi, especially insects, acarids and nematodes, with other andfurther objects becoming apparent from a study of the withinspecification and accompanying examples.

From German Published Specification 1,253,713 it is known thathalogen-substituted benzisoxazolothionophosphoric (phosphonic) acidesters, such as 0,0-dimethylor diethyl O[5-chlorobenzisoxazol(3)yl]-thionoph0sphoric acid ester, exhibit aninsecticidal activity.

' The present invention provides, as new compounds, thebenzisoxazolo(thiono)phosphoric(phosphonic) acid esters of the generalformula in which R is a lower alkyl radical,

R is a lower alkyl or alkoxy radical, and X is an oxygen or sulfur atom.

3,828,063 Patented Aug. 6, 1974 phonic) acid ester of the formula (I) inwhich 3-hydroxy- 1,2-benzisoxazole of the formula (5H (II) is reacted,in the presence of an acid-acceptor or in the form of an appropriatealkali metal salt, alkaline earth metal salt or ammonium salt, with a(thiono) phosphoric (phosphonic) acid ester halide of the generalformula in which R, R and X possess the meaning stated above, and Hal isa halogen atom.

Surprisingly, the benzisoxazole (thiono) phosphoric (phosphonic) acidesters according to the invention show a considerably higherinsecticidal and acaricidal activity than the known halogen-substituedbenzisoxazolo(thiono) phosphoric acid esters which are the chemicallymost closely comparable active compounds of the same direction ofactivity. The substances according to the invention therefore representa genuine enrichment of the art.

If 3-hydroxy-1,2-benzisoxazole and 0,0-diethylthionophosphoric acidester chloride are used as starting materials, the reaction course canbe represented by the following equation:

H acid acceptor I Cl-P 0 can), \/N -HCl I (II) OH (IIIa) I N 1 i O P (0Calls) Advantageously the alkyl or alkoxy groups of R and R contain 1 to4 carbon atoms and, preferably, R is methyl or ethyl and R is methyl,ethyl, methoxy or ethoxy; Hal is preferably a chlorine atom.

As examples of (thiono)phosphoric(phosphonic) acid ester halides (III)which can be used, there may be mentioned: 0,0-dimethyl-, 0,0-diethy1-,0,0-diisopropyl-, O-methyl-O-ethyl-, O-ethyl-O-isopropyland O-methylO-isopropyl-phosphoric acid ester halides and their thiono analogues;further, O,P-dimethyl-, O,P-diethyl-, O,P-diisopropyl,O-methyl-P-ethyl-, O-methyl-P-isopropyl-, O- isopropyl-P-ethylandO-isopropyl-P-methyl-phosphonic acid ester halides and their thionoanalogues.

The (thiono) phosphoric (phosphonic) acid ester halides as well as the3-hydroxybenzisoxazole to be used as starting materials can be preparedaccording to known processes.

The reaction may be carried out in a solvent or diluent; practically allinert organic solvents are suitable.

Preferred solvents are aliphatic and aromatic optionally are suitable.Especially suitable are alkali metal carbonates and alcoholates, such assodium or potassium carbonate and sodium or potassium methylate orethylate; furthermore, aliphatic, aromatic or heterocyclic amines, forexample triethylamine, dimethylamine, dimethylaniline,dimethylbenzylamine or pyridine, may be used.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reactants are mixed at about to 50 C., preferably at aboutto C. and the mixture is afterwards stirred at about to 120 C.,preferably at about 70 to 80 C.

The reaction is, in general, carried out at normal pressure.

When carrying out the process, the starting materials are, in mostcases, reacted in eqnimolar amounts in one of the above-mentionedsolvents at elevated temperatures. An excess of one or other of thereactants brings no substantial advantages. The heterocyclic reactantcan also be used in the form of its alkali metal salts, alkaline earthmetal salts or ammonium salt, as already mentioned. The reactionsolution is in most cases afterwards stirred for some hours at elevatedtemperatures, taken up in benzene and worked up as usual.

The esters according to the invention are obtained in most cases in theform of colorless to slightly yellow-colored, viscous, water-insolubleoils which cannot be distilled without decomposition but can, byso-called slight distillation, that is by prolonged heating tomoderately elevated temperatures under reduced pressure, be freed fromthe last volatile components and in this way be purified. For theircharacterization, the refractive index is especially useful.

The new compounds according to the invention are distinguished byoutstanding nematocidal, insecticidal and acaricidal properties. Theyare eflective against both sucking and biting insects, Diptera, mites,as well as a systemic activity. Additionally, some of them also showfungitoxic effectiveness against phytopathogenic fungi. The products maytherefore be used with success in crop protection and in the protectionof stored products, as well as in the hygiene field, against the mostdiverse animal pests.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid Doralz's fabae), the bird cherry aphid (Rhopalosz'phum padi),the pea aphid (Macrosiphum psi) and the potato aphid (Macrosiphumsolanifolii), the current gall aphid (Cryptomyzus korschelti), the rosyapple aphid (Sappaphis mall), the mealy plum aphid (Hyaloptemsarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex lectularius), the assassin bug (Rhodm'us prolixus) and Chagas bug(Triatoma inf estans) and, further cicadas, such as Euscelis bilobamsand Nephotettix bipunctatus; and the like.

. In the case of the biting insects contemplated herein,

above all there should be mentioned butterfly caterpillars (Lepidoptera)such as the diamond-back moth (Plutella maculipennis), the gpysy moth(Lymzmtria dispar), the

brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar(Malacosoma neustria); further the cabbage moth (Mante -rm brassicae)and the cutworm (Agrotis sege- 4v Also to beclassed with the bitinginsects contemplated herein are beetles (Coleoptera), for example thegranary Weevil (Sitophilus granarius=Calandra granaria), the Coloradobeetle (Leptinostarsa decemlineata), the dock beetle (Gastrophysaviridula), the mustard beetle (Phaedon cochleariae), the blossom beetle(Meligethes aeneus), the raspberry beetle (Byturus tOmentoSus), the beanweevil (Bruchidius=Acanthoscelide obtectus), the leather beetle(Dermestes frischi), the khapra beetle (Tr'o'godermal grzmarium), theflour beetle (T ribolium castane um), the northern corn billbug(Calandra or Sito'philus zeamais), the drugstore beetle (Stegobiump'aniceum the yellow mealworm (Tenebrio molitor) and the sawtoothedgrain beetle (Oryzaephilus surinamensis), and also species living in thesoil, for. example wireworms (Agriotes spec.) and larvae of thecockchafer (Melolontha melolontha); cockroaches, such as the Germancockroach (Blattella germanica), American cockroach (Periplanetaamericana), Madeira cockroach (Leucophaea or Rhyparobia m'adeirae),oriental cockroach (Blatta orientalis), the giant cockroach (Blaberusgiganteus) and the black giant cockroach (Blaberus fuscus) as well asHenschoutedenia flexivl'tta; further, Orthoptera, for example the housecricket (Acheta domesticu-s); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptem such as ants, forexample the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophz'la'melanogdster), the Mediterranean fruit fly(Cemtitis capitara), the house fly (Musca domestica), the little housefly (Fanm'a canicularis), the black blow fly (Phormia aegina) andbluebottle fly (Calliphora erythrocephala) as Well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius=Tetranychus althaeae or Tetranychusurticae) and the European red mite (Paratetranychus pilosus: Panonychusulmi), gall mites, for example the black current gall mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the 'cyclamen mite (Tarsonemus pallz'dus); finally, ticks,such as the relapsing fever tick (Ornithodorous moubata); and the like.a

When applied against hygiene pests harmful to health and to storedproducts, particularly flies and mosquitoes, the novel products are alsodistinguished by an outstanding residual activity on wood and clay, aswell as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicle such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, eJg. conventional pesticide surface-activeagents,' including emulsifying agents and/or dispersing agents whereby,for

example, in the case where water is used as. diluent, or-

ganic solvents may vbe-added as auxiliary solvents. .The following maybe chiefly considered for'use asiconventional carrienvehicles for thispurpose: aerosol propellants which are-gaseous at normal temperaturesandvpressures,

such as freon; inert dispersible liquid diluent carriers, includinginert organic solvents, such as aromatic hydrocarbons (e.g. benzene,toluene, xylene, etc.), halogenated, especially chlorinated, aromatichydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleumfractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride,etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.),amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycolmonomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone,etc.), and/ or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, clays, alumina,silica, chalk, i.e. calcium carbonate, talc, attapulgite,montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g.highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.);whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g. surface-active agents, for thispurpose: emulsifying agents, such as non-ionic and/or anionicemulsifying agents (e.g. polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, arylsulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesiumstearate, sodium oleate, etc.); and/or dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/ or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides, fungicides, bactericides and nematocides, or rodenticides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use. I

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 0.5-90% by weight, of the mixture, whereas carriercompositionmixtures suitable for direct application or field applicationgenerally contemplate those in which the active compound is present inan amount substantially between about 0.0001-%, preferably 0.011%, byweight of the mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. a surfaceactive agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.000l-95%, and preferably 0.0l95%, by weightof the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/ hectare are needed,and often amounts only up to about to 1000 g./hectare, preferably 40 to600 g./hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95% by weight of the activecompound or even the 100% active substance alone, e.g. about 20 100% byweight of the active compound.

furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids,nematodes and fungi and more particularly methods of combating at leastone of insects, acarids and nematodes which comprises applying to atleast one of correspondingly (a) such insects, (b) such acarids, (c)such nematodes, (d) such fungi, and (e) the corresponding habitatthereof, i.e. the locus to be protected, a correspondingly combative ortoxic amount, i.e. an insecticidally, acaricidally, nematocidally orfungicidally elfective amount of the particular active compound of theinvention alone or together with a carrier vehicle as noted above. Theinstant formulations or compositions are applied in the usual manner,for instance by spraying, atomizing, vaporizing, scattering, dusting,watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Ceratitis test Solvent: 3 parts by weight acetone Emulsi-fier:1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.

2 cc. of the preparation of the active compound are pipetted on to afilter paper disc of about 10 cm. diameter. This is placed on a glass inwhich there are about 30 friuit flies (Ceratitis capitata) and coveredwith a glass p ate.

After the specified periods of time, the destruction is determined as apercentage. means that all the dwere killed; 0% means that none of theflies were The active compounds, the concentrations of the activecompounds the evaluation times and the results can be seen from Table 1.

o 0 N or o 7 TABLE 1Continued Concentration of Degree of activedestruction compound in percent Active compounds in percent after 1 day(2) 0. 02 100 O 0.004 100 I 0.0008 100 N i Y (CHi):P

(1).... 0.02 100 O 0. 004 100 I 0.0008 100 N 0. 00016 25 2 & )2

EXAMPLE 2 Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1part by weight alkylaryl polyglycol ether.

To product a suitable preparation of active compound, 1 part by weightof the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier and the concentrate isdiluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis) After thespecified periods of time, the degree of destruction is determined as apercentage: 100% means that all the caterpillars are killed whereas 0%means that none of the caterpillars are killed.

The active compounds, the concentrations of the active campounds, theevaluation times and the results can be seen from Table 2:

TABLE 2 (Plutella test) 4 Concentration of Degree of activecorndestruction pound in in percent Active compounds percent atteradaysN Cl ll (CgHsOhP-O r (known) (A)-.. 0.004 100 I)- 0.00s 40 N 01 Hamour-m (known) 0 0. 0008 100 0.00010 00 6a N 3 Y 01100)?- e 0.004. 100U l) 0.0008 70 N ii \I/ c H 0 P-O a s )2 V 8 EXAMPLE 3 c Piesma test 0 ISolvent: 3 parts by Weight acetone. a Y Emulsifier: 1 part by weightalkylarylpolyglyeol ether...

all the beet leaf bugs were killed. 0% means that noneofi the beet leafbugs were killed. 7 v The active compounds, the concentrations of theactive compounds, the evaluation time and the results can be seen fromthe following Table 3:

TABLE 3 (Piesma. test) Concentratlon of Degree of active com- Idestruction pound in in percent Active compounds percent after 3 days(B).-- 0.004 0.0008 20 N 01 i (C:H5O)zP-O (known) 1) 0.004 100 ('J-0.0008 70 N E Y amma?- EXAMPLE 4 Euscelis test Solvent: 3 parts byweight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof the active compound is mixed-with the stated amount of solventcontaining the stated amount of emulsifier and the. concentrate isdiluted with water to the desired concentration. 1 Broad bean plants(Vicia-faba) are sprayed withlthe' preparation of the active compounduntil dew moist are then infested with cicadas ,(Euscelis bilobatits).After the specified period of time, the degree of destruc tion isdetermined as a percentage.100% means that all the cicadas were killedwhereas 0% means that none of the cicadas were killed. i i 1 The activecompounds, the concentrations of the "active compounds, the evaluationtime and the results can be seen from the following Table 4:

TABLE 4 (Euscelis test) Concentra- Degree o tion of destruction compoundin in percent Active compounds percent after 3 days 01 i (CH OhP-i)(known) (C)-.. 0. 1 100 (l) 0. 02 50 N 01 o II 6 (C2H50)gP- (known)(2).-.- 0. 1 100 O 0.02 100 I 0. 004 60 N I (C11 l i) (1) 0. 1 100 O 0.02 100 I 0. 004 100 0, 0008 100 i 2 s i' I 2H50)g1 (4)---- 0.1 100 O0.02 100 I 0. 004 100 N 2115 S \t t fl sO EXAMPLE 5 Doralis test(systemic action) Solvent: 3 parts by weight acetone Emulsifier: 1 partby weight alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.

Bean plants (Vicia faba) which have been heavily infested with the beamaphid (Doralz's fabae) are watered with the preparation of the activecompound so that the preparation of active compound penetrates into thesoil without wetting the leaves of the bean plants. The active compoundis taken up by the bean plants from the soil and thus reaches theinfested leaves.

After the specified period of time, the degree of destruction isdetermined as a percentage. 100% means that all the aphids are killed;0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theevaluation time and the results can be seen from the following Table 5:

TABLE 5 (Doralis test/systemic action) Concentration of Degree of activecomdestruction pound in in percent Active compounds percent after 3 daysCl fi (CHaO) P-) (known) 01 i a a )2 -O (known) (2)-... 0, 1 100 I 90 Nis a0)2 l N I (CgHb0)q-$ N u 2 s )2P'() EXAMPLE 6 Tetranychus testSolvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof the active compound is mixed with the stated amount of solventcontaining the stated amount of solvent containing the stated amount ofemulsifier and the concentrate so obtained is diluted with water to thedesired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately1030 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus 1 1 obtained is expressed as apercentage: 100% means that all the spider mites are killed whereasmeans that none of the spider mites are killed.

The active compounds. the concentrations of the active compounds, theevaluation times and the results can pound is determined as a percentageby counting the dead and living test insects. The degree of destructionis 100% when all the test insects have been killed; it is 0% whenexactly as many test'insects are still alive as in the case of thecontrol.

12 The active compounds, the amounts applied and the re sults can beseen from the following Table 7:

5 be seen from the following Table 6:

TABLE 7 (Soil insecticides) 10 Degree 0! destruction in percent with aconcentration of active compound ln p.p.m. of-

TABLE 6 Active compound (constitution) 40 20 1o 5 2.5

Tetranychus test) (1) O 100 100 100 100 75 Ooncentraon of Degree of Nactive 031:1- dfstructlor S PC1111 H H r6011 Active compounds percentafter days Y [I (I) 0,02 20 (4)"-.. o i 100 100 100 75 s N n s (CHrOhP 002H (known) I 0,1 100 0G (1) 0 0,02 95 1 Known comparative agents: N HCl (C)----: O |O)a 0 l i i E c1 o-i oczm (01110) 0 (known) Cam ('3 0,0240 \l l m 40 01 /PO G 8 cans? (OCHQ)I (known) E A PLE 8 X M EXAMPLE 7Critical concentration test/soil insects Cnmal concentration test Testinsect: cabbage root fly maggots (Phorbia brassicae) 55 ;39 :33 2;g xgqigfg 1 Solvent: 3 parts by weight acetone g Emulsifiep 1 part by weightalkylaryl poly glyc o1 ether Emuls fier. 1 part by weightalkylarylpolyglycol ether.

To produce a suitable preparation of active compound, To Produce asuitable Preparatwn of active c p 1 part by weight of active compound ismixedwith the 1 P y Weight 0f tive compound is mixed With th statedamount of solvent, the stated amount of emulsifier stated amount ofsolvent, the stated amount of emulsifier 5|) is added and theconcentrate is diluted with water to the is added and the concentrate isdiluted with water to the desired concenration. I desired concentration.The preparation of-active compound The preparation of active compound isintimately mixed is intimately mixed with soil. The concentration of thewith soil which is heavily infested with the test nematodes. activecompound in the preparation is of practically no The concentration ofthe active compound in the preparaimportance; only the amount of activecompound per unit tion is of practically no importance; only the amountof volume of soil, which is given in ppm. (for example active compoundper unit volume of soil, which is given mg./l.), is decisive. The soilis filled into pots and the pots in p.p.m., is decisive. The soilisfilled into pots, lettuce is are left to stand at room temperature.After '24 hours, the sown in and the pots are kept-at a greenhousetemperature test animals are put into the treated soil and, after afurther of 27 C. After 4 Weeks, the lettuce roots are examined 48'hours,the degree of effectiveness of the active com- 7 for infestation withnematodes, and the degree of destruction of the active compound isdetermined as a percentage. The degree of effectiveness is wheninfestation is completely avoided; it is 0% .When the infestation isexactly the same as in the case of .the controlplants in untreated soilwhich has been infested in the same manner.

TABLE 8 (Nematocldes/Meloidogyne incognito) Degree of destruction inpercent with a concentration of active compound in p.p.m. oi

Active compound (constitution) II O-P (O OzHsh (known) N C S $i CH1) 2(known) EXAMPLE 9 L'Dmn test Test animals: Blatta orientalis Solvent:acetone.

2 parts by weight of the active compound are dissolved in 1000 parts byvolume of the solvent. The solution so obtained is diluted with furthersolvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. test animals are then placed in thePetri dish and it is covered with a glass lid.

The condition of the test animals is observed 3 days after thecommencement of the experiments. The destruction is determined as apercentage.

The active compounds, the concentrations of the active compounds, thetest animals and the results can be seen from the following Table 9:

14 EXAMPLE 1o Mosquito larvae test Test insects: Aedes aegypti (5thlarval stage) Solvent: 99 parts by weight acetone Emulsifier: 1 part byweight benzylhydroxydiphenyl polyglycol ether.

To produce a suitable preparation of active compound, 2 parts by weightof the active compound are dissolved in 1000 parts by volume of thesolvent containing the amount of emulsifier stated above. The solutionthus obtained is diluted with water to the desired lower concentrations.

The aqueous preparations of the active compounds are placed in glassvessels and about 25 mosquito larvae are then placed in each glassvessel.

After 24 hours, the degree of destruction is determined as a percentage.100% means that all the larvae are killed. 0% means that no larvae atall are killed.

The active compounds, the concentrations of the active comlpounds, thetest insects and the results can be seen from Table 10:

TAB LE 10 (Mosquito larvae test) Concentration of active compound inDegree of the solution destruction Active compound in percent in percent(A). 0. 001 100 0 0. 0001 100 I 0. 00001 01 N Y? 1 (0 0 Ha) I (known)(2) 001 O 0. 0001 100 0. 00001 100 N 0. 000001 90 i --P- 0 CH3) 2EXAMPLE 1 l LDIOO test Test insects: Sitophilus granarius (granaryweevils) Solvent: acetone.

2 parts by weight of the active compound are dissolved in 1000 parts byvolume of the solvent. The solution so obtained is diluted with furthersolvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a tfilter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used.

TABLE 11 (LD no test) Concentratlon of active Destrucccmpound tion inActive compounds in percent percent (A). 0.2 100 O 0. 02 l 0. 002 0 C Ni -P(O CH2) 2 (known) (B)..- 0.2 100 O 0. 02 100 I $683.3. "8 01- N(known) (2).--. 0.2 100 O 0. 02 100 I 0. 002 100 N 0. 0002 100 0. 0000230 3 P(O C H3) 1 EXAMPLE 12 L'I' test for Diptera Test animals: Aedesaegypti Solvent: acetone.

2 parts by weight of active compound are dissolved in 1000 parts byvolume of solvent. The solution so obtained is diluted with furthersolvent to the desired concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petridish. On the bottom of the Petri dish. there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test animals are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test animals is periodically observed. The timewhich is necessary for a. 100% destruction is determined.

The test animals, the active compounds, the concentrations of the activecompounds and the periods of time 16 at which there is a destruction canbe seen from the following Table 12:

TABLE 12 mo test for Diptera) 1 Concentration of active compound in thesolution Active compounds in percent LTmo (A) 0. 2 CI) 0. 02 01- N 0 -P(0 CH3):

(known) (B), 0.2 60' 0. 02 120 m- N A) 'P (O C2Hs) 2 (known) v (2) 0. 260' O O. 02 60' I I 0. 002 120; N 0 0002 180 i P (0 C 4) 2 Thepreparative process of the present invention is illustrated in and bythe following Example.

EXAMPLE l3 45 g. of potassium carbonate are added to a solution of 0.3mole (41 g.) of 3-hydroxy-1,3-benzisoxazole in 250 m1. of acetonitrile;75 g. of 0,0-diethylthionophosphoric acid diester chloride are thenadded to 30-35 C. and heating to 7080 C. is efiected for a further 2hours. After cooling, the mixture is taken up in benzene, extracted withwater, the benzene phase is separated, dried, evaporated, and theresidue is slightlydistilled.

The yield is 68 g. =76% of the theory.

Calc. for C H O NSP (molecular weight 287): 10.8%, 11.2%, 4.88%. F0und:10.72%, 11.89%, 4.38%.

The following compounds are prepared by processes analogous to thatgiven above:

Formula Retractive index C (5-1 (0 CH):

Preparation of the starting material S (CHa0)zi (2) 2. 0,? diethyl 0benzisoxazol(3)-yl-thionophosphonic acid ester of the formula 0 It ayC2Hs (4) References Cited FOREIGN PATENTS 965,997 8/ 1964 England.

DONALD G. DAVIS, Primary Examiner R. V. RUSH, Assistant Examiner US. Cl.X.R. 424-200 UNHM) S'I'A'USS lA'lbN'l' UMJ'LQE CERTIFICATE OF CGRRECTIONPatent: No, 3,828,063 Dated August 6, 1974 Q lnvemofls) Walter Lorenz eta1.

It is certified that error appears in the aboye-identified patent andthat said Letters Patent are hereby corrected as shown below: Q I I"'2';

Col, 10, line lZ-Table 5, heading of last column of Table,

cancel "3 days" and substitute 4 days Col. ll, line l9-Table 6, headingof last column of Table,

cancel "3 days" and substitute 2 days Col. ll, Table 6, Compounds (1),(2) and (3), cancel Cl" at the end of each formula.

Col. 16, line 67, cancel "to' and substitute at g and 56211661 this[SEAL] twenty-third Of March 1976 Altest:

:fjligggig" C I cmnsHALL DANN r nts and Tradem k

